EP0072444B1 - Moulding composition for a cross-linked foam of polyolefins and ethylene-propylene rubber, and process for producing the foam - Google Patents

Moulding composition for a cross-linked foam of polyolefins and ethylene-propylene rubber, and process for producing the foam Download PDF

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Publication number
EP0072444B1
EP0072444B1 EP82106447A EP82106447A EP0072444B1 EP 0072444 B1 EP0072444 B1 EP 0072444B1 EP 82106447 A EP82106447 A EP 82106447A EP 82106447 A EP82106447 A EP 82106447A EP 0072444 B1 EP0072444 B1 EP 0072444B1
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European Patent Office
Prior art keywords
weight
ethylene
parts
cross
propylene
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EP82106447A
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German (de)
French (fr)
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EP0072444A1 (en
Inventor
Werner Kühnel
Paul Dr. Spielau
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Huels Troisdorf AG
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Huels Troisdorf AG
Dynamit Nobel AG
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Priority to AT82106447T priority Critical patent/ATE26455T1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/05—Use of one or more blowing agents together
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/18—Cross-linking a thermoplastic linear foam during molding

Definitions

  • the invention relates to a foamable molding composition for producing a crosslinked foam based on a mixture of a polyolefin and an ethylene-propylene rubber, a foaming agent and optionally a crosslinking agent, by pressure-free crosslinking and foaming, a process for producing crosslinked foams with very fine Uniform, predominantly closed cell structure based on a mixture of a polyolefin and an ethylene-propylene rubber.
  • At least one rubber and / or plastic that is miscible with the polyolefin can be incorporated into 100 parts of polyolefin, with rubbers that are miscible with polyolefin, e.g. Natural rubber, ethylene-propylene rubber, butyl rubber, polyisobutylene, styrene-butadiene rubber, polybutadiene, and polyisoprene can be understood.
  • Radiation-crosslinked polyolefin foams are described, for example, in DE-OS 15 69 465, these polyolefin foams being added by adding 5 to 500 parts by weight of rubber such as natural rubber, ethylene-propylene rubber, styrene-butadiene rubber, nitrile-butadiene rubber, polycis -Butadiene rubber, neoprene rubber based on 100 parts by weight of polyethylene can be modified.
  • the modification of crosslinked polyolefin foams by adding rubber or other plastics serves the purpose of transferring in particular the physical properties of the added rubbers or plastics, such as temperature resistance, better mechanical resistance, higher elasticity and tensile strength, to the foam.
  • polystyrene foams The addition of rubbers gives the polyolefin foams greater elasticity.
  • DE-A-19 20 931 discloses foamable polymer compositions of the type according to the invention in which ethylene-propylene rubber instead of large amounts of carbon black, inorganic fillers and plasticizer oils in a ratio of 5 to 95 parts by weight of rubber, 95 to 5 Parts by weight of polyolefins are added, it being possible for the foam qualities that can be produced to be partly soft, partly harder, partly fine-celled, the fine-celledness being achieved when foaming using external pressure.
  • Another effort is to produce very fine cell polyolefin foams.
  • Cell size, uniformity of the closed cells, cell wall structure have a significant influence on the properties of a foam, the finer and more uniform the cell size, the better the thermal insulation and damping properties as well as the appearance - smooth, fine surface - of the foam.
  • the essence of the invention is seen in the fact that by adding selected partially crystalline ethylene-propylene terpolymers with certain properties, crosslinked foam materials based on polyolefins can be produced, which not only have the improved physical properties due to the added ethylene-propylene terpolymer rubber, but at the same time surprisingly lead to cell downsizing, ie fine celling.
  • the special partially crystalline ethylene-propylene terpolymers selected according to the invention are suitable for solving the object set according to the invention, ie producing a smooth surface and finer cells compared to the known polyolefin foams.
  • the selected ethylene-propylene terpolymers affect both the processability and the quality of the foam produced are favorable.
  • the partial crystallinity is essential for the selection of the ethylene-propylene terpolymers, about which the melting curves measured by the DSC method in the differential scanning calorimeter provide information.
  • the maximum of the melting peak, measured as the temperature TS in ° C by the DSC curve is referred to as the endothermic peak to the high e n be, or may also comprise an area g.
  • the temperature TS is in the range around 50 ° C.
  • the amount of heat required for melting the so-called heat of fusion ⁇ H S, also measured by the DSC method, provides information about the presence of crystalline blocks in the ethylene-propylene terpolymer.
  • Such partially crystalline ethylene-propylene terpolymers with a heat of fusion of at least 10 J / g are used according to the invention.
  • the crosslinked foam bodies produced with the foamable molding composition according to the invention which are either chemically crosslinked by means of a crosslinking agent or are crosslinked by means of high-energy radiation, have on average 2 to 5 times the number of cells compared to polyolefin foams on the same basis without the ethylene propylene added according to the invention.
  • the pore size or cell size of the foam material is to be considered relatively, it is also always dependent on the density of the foam and the thickness of the foam sheet or parts produced. The higher the density of a foam, the smaller the cells and the thicker a foam sheet, the larger the cells, under otherwise identical conditions.
  • crosslinking can be used for the foams crosslinked according to the invention.
  • One possibility is the use of high-energy radiation, in which case a foamable molding compound is exposed to ionizing radiation.
  • the other way is to use a crosslinking agent.
  • suitable crosslinking agents for the invention are peroxides, in particular dicumyl peroxide, but also 2,5-dimethyl-2,5- (tertiary-butyl) -peroxyhexane, 1,10-decane-bis-sulfonacide, p-quinone dioxin and others.
  • crosslinking agents are preferred in amounts of 0.6 to 1.6 parts by weight, based on the sum of 100 parts by weight of polyolefin and 25 to 150 parts by weight of a partially crystalline ethylene-propylene terpolymer selected in accordance with the invention foamable molding compound provided.
  • a preferred foaming agent in the process and the molding composition according to the invention is a foaming agent whose decomposition temperature is equal to or higher than that of the crosslinking agent.
  • Azodicarbonamide and its derivatives are particularly preferred, but foaming agents such as dinitrosopentamethylenetetramine, p, p-oxy-bis-benzenesulfonylhydrazide and toluenesulfonylhydrazide are also suitable.
  • the amount of foaming agent to be used depends on the desired bulk density of the foam to be produced and is generally between 0.5 and 25% by weight, based on the total foamable molding composition. It can be used to produce foams with densities of 25 to 300 kg / m 3 and more.
  • the preferred polyolefins are polyethylene with a melt index (MFI 190/2) of 1 to 8 and a density of 0.91 to 0.96 g / cm 3 , preferably high-pressure polyethylene.
  • MFI 190/2 melt index
  • copolymers preferably those for the preparation of which monomer mixtures with a predominant proportion of ethylene have been used, and their mixtures with homopolymers can also be used for the invention.
  • additives which are usually used together with polyolefin-based plastics such as light stabilizers, pigments, fillers, flame retardants, antistatic agents, lubricants, etc., can be added to the foamable and crosslinkable molding composition before processing.
  • the molding composition according to the invention is described in more detail below.
  • Semi-crystalline ethylene-propylene terpolymers with high strength which are also known as high green strength rubbers, are preferably used, which have a tensile strength above 8 N / mm 2 up to 20 N / mm2 and more.
  • the selected ethylene-propylene terpolymers should also have very good processability, which is why ethylene-propylene terpolymers with a Mooney viscosity ML 1 +4/100 greater than 50 are selected.
  • Ethylene-propylene terpolymers with 65 to 80% by weight of ethylene, 4 to 10% by weight of ter component and 10 to 31% by weight of propylene are particularly suitable.
  • Ethylene-propylene terpolymers with a ter component of ethylidene norbornene or 1,4-hexadiene have proven to be particularly suitable.
  • the desired fine cell structure of the crosslinked foam according to the invention is achieved by adding minimum amounts of the selected partially crystalline ethylene-propylene terpolymer, with at least 25 parts by weight being required based on 100 parts by weight of polyolefin. 25 to 60 parts by weight of ethylene-propylene terpolymers per 100 parts by weight of polyolefin are preferably used.
  • polyethylene is an inexpensive plastic compared to an ethylene-propylene terpolymer and the crosslinked polyolefin foams which can be produced according to the invention are economical with a lower proportion of ethylene-propylene terpolymer.
  • a particular advantage of the process according to the invention is that foam sheets based on polyolefins and ethylene-propylene rubber with very fine cells with a homogeneous quality and smooth surface can be produced continuously without the use of external pressure or molding.
  • This temperature treatment can either be brief, it is then preferably carried out at below the decomposition temperature of the crosslinking agent, in particular at a temperature between about 90 and 110 ° C for 2 to 90 minutes, or at room temperature, i.e. about 15 to 20 ° C for a period of at least 1 day.
  • the latter procedure means, for example, that the shaped mixture can be stored before it is subsequently subjected to crosslinking and foaming.
  • the process according to the invention can be used to produce crosslinked polyolefin foams with a very high degree of fine cell and homogeneity, low wall thicknesses, a closed surface and high elasticity and softness in the handle. Furthermore, the properties of the foam which can be produced using the molding composition according to the invention and by the processes described are significantly improved compared to polyolefin foams without the addition of the ethylene-propylene terpolymers selected according to the invention, in particular with regard to compressive stress, dynamic perforation and thermal insulation and elongation at break.
  • the foams produced according to the invention can advantageously be used for the production of molded parts by vacuum forming, since they have good heat deformability and for demanding thermal insulation at elevated temperatures.
  • crosslinked foams which can be produced according to the invention have, with good temperature resistance and very high fine cell structure, an unexpectedly high ductility and excellent processability for vacuum deformation in the deep-drawing process and similar deformation processes.
  • the foamable molding composition according to the invention requires relatively low amounts of crosslinking agent, for example peroxides, in order to achieve sufficient crosslinking in the production of the crosslinked foam.
  • crosslinking agent for example peroxides
  • a cross-linked foam is usually not 100% cross-linked, but between 40 and 80%.
  • the degree of crosslinking is measured here, for example, when the crosslinked foam is extracted for twelve hours at 135 ° C. using tetrahydronaphthalene as the solution extractant in the gel content.
  • the gel content in the foams produced according to the invention should then be between 40 and 80% by weight.
  • the foamable molding composition according to the invention is particularly easy to process due to the intended selection of materials, i.e. extrudable, so that a homogeneous mixture and shaping of the foamable molding compound can be made to the sheet or profile.
  • the rolled skin obtained is in the press at 130 ° C, 50 bar and a standing time of 8 min. smoothed. Samples of 8 cm 0 are punched out of this plate and these are then foamed into foam bodies in a drying cabinet at a temperature of 210 ° C. The unfoamed panels had a thickness of 4 mm.
  • the samples can also be produced by mixing the recipe on continuous compounding systems, the granules then obtained being subsequently extruded on a slot extruder to form a matrix which is then foamed in an, for example, heatable channel to form an endless foam web with crosslinking.
  • Examples 1, 2 and 12 are the comparative examples.
  • Example 1 a normal polyethylene foam with bulk density of 30 kg / m 3 without EPDM and gem.
  • B the foam produced according to the invention from a molding composition with the addition of 30 parts by weight of EPDM, density 38 kg / m 3 according to Example 3. This foam is very fine-celled and has a smooth surface.
  • Examples 13 to 22 are listed, which, starting from the same mixture of high-pressure polyethylene and EPDM with crosslinking agent, only vary the amounts of foaming agent, as a result of which foam bodies of different high densities are produced. In all cases it can be seen that the desired fine cell structure can be produced with a smooth surface.
  • the raw materials used correspond in their qualifications to the raw materials described in Examples 1 to 10.
  • Table 3 shows the properties of a crosslinked polyethylene foam without EPDM addition with a bulk density of 130 kg / m 3 of Comparative Example 12 with a foam body according to the invention containing 30 parts by weight.
  • EPDM compiled on 100 parts by weight of polyethylene with the same bulk density according to Example 11. It follows from this that with comparable foams, namely the same bulk density, the foams according to the invention have significantly better properties with regard to strength and extensibility and elasticity.
  • the foams according to the invention are therefore particularly suitable for the production of molded parts, for example by vacuum forming, deep-drawing molding, etc. In addition, they have improved insulating properties.
  • Example 23 with 20 parts by weight of ethylene terpolymer is a comparative example.
  • the achievable cell size, and thus the cell structure of the foam is dependent both on the formulation, i.e. the recipe components, as well as the foam body size to be foamed.
  • the cell size that can be achieved always depends on the density of the foam to be produced and on the thickness of the mixture which has not yet been foamed. It is the case that with increasing spatial density and otherwise constant parameters, the cells become smaller and smaller. On the other hand, as the thickness of the molded mixture which has not yet been foamed increases, the cells become ever larger with the same parameters.
  • FIG. 2 shows the dependence of the achievable average cell diameter on the bulk density of a polyolefin foam without (curve I) and with the addition according to the invention of 40% by weight of ethylene-propylene terpolymer (curve II) as described in Examples 1 to 10 at a thickness of the molded, not yet foamed sheet of 4 mm.

Abstract

An expandable molding composition for the production of a cross-linked foam material, and a process for the manufacture of the foam from a mixture of polyolefin and a selected, partially crystalline ethylene-propylene terpolymer, a blowing agent, and optionally a crosslinking agent are disclosed.

Description

Die Erfindung bezieht sich auf eine verschäumbare Formmasse zum Herstellen eines vernetzten Schaumstoffes auf Basis eines Gemisches eines Polyolefins und eines Äthylen-Propylen-Kautschuks, eines Schäummittels und ggf. eines Vernetzungsmittels, durch druckloses Vernetzen und Verschäumen ein Verfahren zum Herstellen von vernetzten Schaumstoffen mit sehr feiner gleichförmiger überwiegend geschlossener Zellstruktur auf Basis eines Gemisches eines Polyolefins und eines Äthylen-Propylen-Kautschuks.The invention relates to a foamable molding composition for producing a crosslinked foam based on a mixture of a polyolefin and an ethylene-propylene rubber, a foaming agent and optionally a crosslinking agent, by pressure-free crosslinking and foaming, a process for producing crosslinked foams with very fine Uniform, predominantly closed cell structure based on a mixture of a polyolefin and an ethylene-propylene rubber.

Es ist bekannt, Polyolefine mit Peroxyden und/oder energie reichen Strahlen zu vernetzen und gleichzeitig oder anschließend mit chemischen Schäummitteln wie z.B. Azodicarbonamid, Sulfonylhydrazin, Sulfonylsemicarbaziden und dgl. aufzuschäumen (siehe beispielsweise DE-AS 16 94130).It is known to crosslink polyolefins with peroxides and / or high-energy rays and simultaneously or subsequently with chemical foaming agents such as e.g. Foaming azodicarbonamide, sulfonyl hydrazine, sulfonyl semicarbazides and the like (see for example DE-AS 16 94130).

Hierbei können bis zu 100 Gew.-Teile mindestens eines mit dem Polyolefin mischbaren Kautschuks und/oder Kunststoffs auf je 100 Teile Polyolefin eingearbeitet werden, wobei unter mit Polyolefin mischbare Kautschuke z.B. Naturkautschuk, Äthylen-Propylen-Kautschuk, Butylkautschuk, Polyisobutylen, Styrolbutadienkautschuk, Polybutadien, und Polyisopren verstanden werden.Up to 100 parts by weight of at least one rubber and / or plastic that is miscible with the polyolefin can be incorporated into 100 parts of polyolefin, with rubbers that are miscible with polyolefin, e.g. Natural rubber, ethylene-propylene rubber, butyl rubber, polyisobutylene, styrene-butadiene rubber, polybutadiene, and polyisoprene can be understood.

Strahlenvernetzte Polyolefinschaumstoffe werden beispielsweise in der DE-OS 15 69 465 beschrieben, wobei diese Polyolefinschaumstoffe durch Zusatz von 5 bis 500 Gew.-Teilen Kautschuk wie Naturkautschuk, Äthylen-Propylen-Kautschuk, Styrol-Butadien-Kautschuk, Nitril-Butadien-Kautschuk, Polycis-Butadien-Kautschuk, Neopren-Kautschuk bezogen auf 100 Gew.-Teile Polyäthylen modifiziert werden können. Die Modifizierung vernetzter Polyolefinschaumstoffe durch Zusatz von Kautschuk oder anderen Kunststoffen dient dem Zweck, insbesondere die physikalischen Eigenschaften der zugesetzten Kautschuke, bzw. Kunststoffe, wie Temperaturbeständigkeit, bessere mechanische Widerstandsfähigkeit, höhere Elastizität und Zugfestigkeit auf den Schaumstoff zu übertragen. Der Zusatz von Kautschuken verleiht hierbei den Polyolefinschaumstoffen eine höhere Elastizität. Beispielsweise ist es auch bekannt (siehe DE-AS 28 39 733 und DE-OS 30 32 635) temperaturbeständigere vernetzte Polyolefinschaumstoffe auf Basis von Polypropylen herzustellen. Weiterhin ist es bekannt, vernetzte Polyolefinschaumstoffe zum Herstellen von sehr leichtgewichtigen Schaumstoffen durch Zusatz von Polybutadien zu modifizieren (siehe DE-AS 19 30 134 und DE-OS 29 11 719).Radiation-crosslinked polyolefin foams are described, for example, in DE-OS 15 69 465, these polyolefin foams being added by adding 5 to 500 parts by weight of rubber such as natural rubber, ethylene-propylene rubber, styrene-butadiene rubber, nitrile-butadiene rubber, polycis -Butadiene rubber, neoprene rubber based on 100 parts by weight of polyethylene can be modified. The modification of crosslinked polyolefin foams by adding rubber or other plastics serves the purpose of transferring in particular the physical properties of the added rubbers or plastics, such as temperature resistance, better mechanical resistance, higher elasticity and tensile strength, to the foam. The addition of rubbers gives the polyolefin foams greater elasticity. For example, it is also known (see DE-AS 28 39 733 and DE-OS 30 32 635) to produce more temperature-resistant crosslinked polyolefin foams based on polypropylene. Furthermore, it is known to modify crosslinked polyolefin foams for producing very lightweight foams by adding polybutadiene (see DE-AS 19 30 134 and DE-OS 29 11 719).

Aus der DE-A- 19 20 931 sind verschäumbare Polymerisatmassen der erfindungsgemäßen Gattung bekannt, bei denen Äthylen-Propylen-Kautschuk an Stelle von großen Mengen Ruß, anorganischen Füllstoffen und Weichmacherölen im Verhältnis von 5 bis 95 Gew.-Teilen Kautschuk, 95 bis 5 Gew.-Teile Polyolefine zugegeben werden, wobei die herstellbaren Schaumqualitäten teils weich, teils härter, teils feinzellig sein können, wobei die Feinzelligkeit bei Verschäumen unter Anwendung von äußerem Druck erzielt wird.DE-A-19 20 931 discloses foamable polymer compositions of the type according to the invention in which ethylene-propylene rubber instead of large amounts of carbon black, inorganic fillers and plasticizer oils in a ratio of 5 to 95 parts by weight of rubber, 95 to 5 Parts by weight of polyolefins are added, it being possible for the foam qualities that can be produced to be partly soft, partly harder, partly fine-celled, the fine-celledness being achieved when foaming using external pressure.

Ein weiteres Bemühen besteht darin, sehr feinzellige Polyolefinschaumstoffe herzustellen.Another effort is to produce very fine cell polyolefin foams.

Hierzu wird gemäß DE-AS 23 51 515 bei einem Verfahren zum Herstellen feinzelliger Schaumstoffe aus Polyolefinen durch peroxydische Vernetzung und Verschäumen durch ein Treibmittel vorgeschlagen, dem Polyolefin außer dem Peroxyd und dem Treibmittel als Hilfsmittel ein weiteres Treibmittel mit einem niedrigeren Temperaturzersetzungsbereich als das erste Treibmittel zuzusetzen, um auf diese Weise eine Zellverkleinerung und damit feinzelligeren Schaumstoff zu erzielen.For this purpose, according to DE-AS 23 51 515 in a process for producing fine-cell foams from polyolefins by peroxidic crosslinking and foaming by means of a blowing agent, it is proposed to add another blowing agent with a lower temperature decomposition range than the first blowing agent to the polyolefin in addition to the peroxide and the blowing agent in order to achieve cell reduction and thus more fine-cell foam.

Nach der DE-OS 23 48 468 wird ein Verfahren zum Herstellen vernetzter Polyolefinschaumstoffe mit sehr feiner und gleichförmiger geschlossener Zellstruktur vorgeschlagen, bei dem die Feinzelligkeit mit Hilfe eines Verschäumungsmittels mit einem mittleren Teilchendurchmesser von 10 bis 30 11m erreicht werden soll, wobei als Verschäumungsmittel z.B. Azodicarbonamid in Frage kommt.According to DE-OS 23 48 468, a method for producing crosslinked polyolefin foams with a very fine and uniform closed cell structure is proposed, in which the fine cell structure is to be achieved with the aid of a foaming agent with an average particle diameter of 10 to 30 11 m, the foaming agent being e.g. Azodicarbonamide comes into question.

Zellgröße, Gleichförmigkeit der geschlossenen Zellen, Zellwandaufbau beeinflussen die Eigenschaften eines Schaumstoffes ganz wesentlich, je feiner und gleichförmiger die Zellgröße ist, desto besser sind die Wärmeisolierungs- und Dämpfungseigenschaften sowie das Aussehen - glatte feine Oberfläche - des Schaumstoffes.Cell size, uniformity of the closed cells, cell wall structure have a significant influence on the properties of a foam, the finer and more uniform the cell size, the better the thermal insulation and damping properties as well as the appearance - smooth, fine surface - of the foam.

Während nach dem Verfahren gemäß dem Stand der Technik jeweils zusätzliche Mittel eingesetzt wurden, um die feinere Zellstruktur eines vernetzten Polyolefinschaumstoffes zu erzeugen, wurde gem. der Erfindung überraschender Weise gefunden, daß auch eine Mischung von Polyolfinen mit ausgewählten Kautschuken einen sehr feinzelligen elastischen Schaumstoff glechmäßiger Zellstruktur ergibt. Die Erfindung löst die gestellte Aufgabe durch eine verschäumbare Formmasse, die auf 100 Gew.-Teile Polyolefin 25 bis 150 Gew.-Teile eines teilkristallinen Äthylen-Propylen-Terpolymers einer Reißfestigkeit größer 5,0 N/mm2, einer Mooney-Viakosität (ML 1 +4/100) größer 50 mit einer Schmelzwärme A Hs größer 10 J/g und mit

  • 60 bis 80 Gew.-% Äthylen,
  • 2 bis 10 Gew.-% Terkomponente aus Äthylennorbornen oder 1,4 Hexadien,
  • 10 bis 38 Gew -% Propylen
  • enthält.
While according to the method according to the prior art each additional means were used to produce the finer cell structure of a crosslinked polyolefin foam, according to. The invention surprisingly found that a mixture of polyol fins with selected rubbers results in a very fine-celled elastic foam with a uniform cell structure. The invention solves this problem by a foamable molding compound which, on 100 parts by weight of polyolefin, contains 25 to 150 parts by weight of a partially crystalline ethylene-propylene terpolymer with a tensile strength greater than 5.0 N / mm 2 , a Mooney via viscosity (ML 1 +4/100) greater than 50 with a heat of fusion AH s greater than 10 J / g and with
  • 60 to 80% by weight of ethylene,
  • 2 to 10% by weight of tere component from ethylene norbornene or 1.4 hexadiene,
  • 10 to 38% by weight propylene
  • contains.

Das Wesen der Erfindung wird darin gesehen, daß durch den Zusatz ausgewählter teilkristalliner Äthylen-Propylen-Terpolymere mit bestimmten Eigenschaften vernetzte Schaummstoffe auf Basis von Polyolefinen herstellbar sind, die nicht nur die aufgrund des zugesetzten Äthylen-Propylen-Terpolymer-Kautschuk verbesserten physikalische Eigenschaften aufweisen, sondern zugleich in überraschender Weise zu einer Zellverkleinerung d.h. Feinzelligkeit führen. Wie noch in den Beispielen gezeigt wird, sind nur die erfindungsgemäß ausgewählten speziellen teilkristallinen Äthylen-Propylen-Terpolymere geeignet, die erfindungsgemäß gestellte Aufgabe zu lösen, d.h. glatte Oberfläche, feinere Zellen gegenüber den bekannten Polyolefinschaumstoffen zu erzeugen. Die ausgewählten Äthylen-Propylen-Terpolymere beeinflussen sowohl die Verarbeitbarkeit als auch die Qualität des hergestellten Schaumstoffes günstig. Wesentlich für die Auswahl der Äthylen-Propylen-Terpolymere ist ihre Teilkristallinität, worüber die nach der DSC-Methode im Differentialabtastcalorimeter gemessenen Schmelzkurven Auskunft geben. Das Maximum des Schmelzpeaks, gemessen als Temperatur TS in °C nach der DSC-Kurve wird als endothermer Peak bezeichnet, der sehr eng sein oder aber auch einen Bereich umfassen kann. Bei Äthylen-Propylen-Terpolymeren liegt die Temperatur TS im Bereich um 50° C. Die zum Schmelzen benötigte Wärmemenge, die sogenannte Schmelzwärme ΔHS gemessen ebenfalls nach DSC-Methode, gibt Aufschluß über das Vorhandensein kristalliner Bläcke im Äthylen-Propylen-Terpolymer. Solche teilkristallinen Äthylen-Propylen-Terpolymere mit einer Schmelzwärme von mindestens 10 J/g werden erfindungsgemäß eingesetzt.The essence of the invention is seen in the fact that by adding selected partially crystalline ethylene-propylene terpolymers with certain properties, crosslinked foam materials based on polyolefins can be produced, which not only have the improved physical properties due to the added ethylene-propylene terpolymer rubber, but at the same time surprisingly lead to cell downsizing, ie fine celling. As will be shown in the examples, only the special partially crystalline ethylene-propylene terpolymers selected according to the invention are suitable for solving the object set according to the invention, ie producing a smooth surface and finer cells compared to the known polyolefin foams. The selected ethylene-propylene terpolymers affect both the processability and the quality of the foam produced are favorable. The partial crystallinity is essential for the selection of the ethylene-propylene terpolymers, about which the melting curves measured by the DSC method in the differential scanning calorimeter provide information. The maximum of the melting peak, measured as the temperature TS in ° C by the DSC curve is referred to as the endothermic peak to the high e n be, or may also comprise an area g. In the case of ethylene-propylene terpolymers, the temperature TS is in the range around 50 ° C. The amount of heat required for melting, the so-called heat of fusion ΔH S, also measured by the DSC method, provides information about the presence of crystalline blocks in the ethylene-propylene terpolymer. Such partially crystalline ethylene-propylene terpolymers with a heat of fusion of at least 10 J / g are used according to the invention.

Die mit der erfindungsgemäßen verschäumbaren Formmasse hergestellten vernetzten Schaumstoffkörper, die entweder chemisch mittels eines Vernetzungsmittels vernetzt sind oder mittels energiereicher Strahlen vernetzt werden, weisen im Durchschnitt die 2 bis 5-fache Zellanzahl auf gegenüber Polyolefinschaumstoffen auf der gleichen Basis ohne die erfindungsgemäß zugesetzten Äthylen-Propylen-Ter-Komponenten. Die Porengröße bzw. Zellgröße des Schsumstoffes ist jeweils relativ zu betrachten, sie ist immer auch abhängig von der Raumdichte des Schaumstoffes und der Dicke der hergestellten Schaumstoffbahn oder Teile. Je höher die Raumdichte eines Schaumstoffes, desto kleiner sind die Zellen und je dicker eine Schaumstoffbahn, desto größer sind die Zellen, bei sonst jeweils gleichen Bedingungen.The crosslinked foam bodies produced with the foamable molding composition according to the invention, which are either chemically crosslinked by means of a crosslinking agent or are crosslinked by means of high-energy radiation, have on average 2 to 5 times the number of cells compared to polyolefin foams on the same basis without the ethylene propylene added according to the invention. Ter components. The pore size or cell size of the foam material is to be considered relatively, it is also always dependent on the density of the foam and the thickness of the foam sheet or parts produced. The higher the density of a foam, the smaller the cells and the thicker a foam sheet, the larger the cells, under otherwise identical conditions.

Bei den erfindungsgemäß vernetzten Schaumstoffen kann jede herkömmliche Art der Vernetzung angewendet werden. Eine Möglichkeit ist die Anwendung von energiereichen Strahlen, in diesem Fall wird eine verschäumbare Formmasse einer ionisierenden Strahlung ausgesetzt. Die andere Weise sieht die Verwendung eines Vernetzungsmittels vor. Beispiele für geeignete Vernetzungsmittel für die Erfindung sind Peroxyde, insbesondere Dicumylperoxyd, aber auch 2,5-Dimethyl-2,5-(Tertiär-Butyl)-Peroxyhexan, 1,10-Decan-Bis-Sulfonacide, p-Chinondioxin u.a. Bevorzugt werden diese Vernetzungsmittel in Mengen von 0,6 bis 1,6 Gew.-Teile bezogen auf die Summe von 100 Gew.-Teile Polyolefin und 25 bis 150 Gew.-Teile eines gemäß der Erfindung ausgewählten teilkristallinen Äthylen-Propylen-Terpolymers in der verschäumbaren Formmasse vorgesehen.Any conventional type of crosslinking can be used for the foams crosslinked according to the invention. One possibility is the use of high-energy radiation, in which case a foamable molding compound is exposed to ionizing radiation. The other way is to use a crosslinking agent. Examples of suitable crosslinking agents for the invention are peroxides, in particular dicumyl peroxide, but also 2,5-dimethyl-2,5- (tertiary-butyl) -peroxyhexane, 1,10-decane-bis-sulfonacide, p-quinone dioxin and others. These crosslinking agents are preferred in amounts of 0.6 to 1.6 parts by weight, based on the sum of 100 parts by weight of polyolefin and 25 to 150 parts by weight of a partially crystalline ethylene-propylene terpolymer selected in accordance with the invention foamable molding compound provided.

Als Schäummittel wird bei dem Verfahren und der Formmasse gemäß der Erfindung ein Schäummittel bevorzugt, dessen Zersetzungstemperatur gleich oder höher ist als diejenige des Vernetzungsmittels. Bevorzugt ist insbesondere Azodicarbonamid und seine Derivate, jedoch kommen auch Schäummittel wie Dinitroso-pentamethylentetramin, p,p-Oxy-bis-benzol-sulfonylhydrazid, Toluolsulfonylhydrazid in Frage. Die anzuwendende Menge an Schäummlttel richtet sich nach der angestrebten Rohdichte des herzustellenden Schaumstoffes und liegt im allgemeinen zwischen 0,5 bis 25 Gew.-% bezogen auf die gesamte verschäumbare Formmasse. Damit können Schaumstoffe mit Raumdichten von 25 bis 300 kg/m3 und mehr hergestellt werden.A preferred foaming agent in the process and the molding composition according to the invention is a foaming agent whose decomposition temperature is equal to or higher than that of the crosslinking agent. Azodicarbonamide and its derivatives are particularly preferred, but foaming agents such as dinitrosopentamethylenetetramine, p, p-oxy-bis-benzenesulfonylhydrazide and toluenesulfonylhydrazide are also suitable. The amount of foaming agent to be used depends on the desired bulk density of the foam to be produced and is generally between 0.5 and 25% by weight, based on the total foamable molding composition. It can be used to produce foams with densities of 25 to 300 kg / m 3 and more.

Als Polyolefine werden für die Erfindung bevorzugt Polyäthylen mit einem Schmelzindex (MFI 190/2) von 1 bis 8. und einer Dichte von 0,91 bis 0,96 g/cm3, vorzugsweise Hochdruck-Polyäthylen vorgesehen. Für die Erfindung können auch Gemische von Polyolefinen z.B. Polyäthylen mit Polypropylen sowie Mischpolymere, vorzugsweise solche, zu deren Herstellung Monomergemische mit überwiegendem Anteil an Äthylen verwendet wurden, sowie deren Gemische mit Homopolymeren eingesetzt werden.For the invention, the preferred polyolefins are polyethylene with a melt index (MFI 190/2) of 1 to 8 and a density of 0.91 to 0.96 g / cm 3 , preferably high-pressure polyethylene. Mixtures of polyolefins, for example polyethylene with polypropylene, as well as copolymers, preferably those for the preparation of which monomer mixtures with a predominant proportion of ethylene have been used, and their mixtures with homopolymers can also be used for the invention.

Des weiteren können auch Zusatzstoffe, die gewöhnlich zusammen mit Kunststoffen auf Polyolefinbasis verwendet werden, wie Lichtschutzmittel, Pigmente, Füllstoffe, flammhemmende Mittel, anstatische Mittel, Gleitmittel usw. der verschäumbaren und zu vernetzenden Formmasse vor der Verarbeitung zugegeben werden.In addition, additives which are usually used together with polyolefin-based plastics, such as light stabilizers, pigments, fillers, flame retardants, antistatic agents, lubricants, etc., can be added to the foamable and crosslinkable molding composition before processing.

Hierbei ist jedoch auf die Verträglichkeit mit der erfindungsgemäßen Formmasse bezüglich der erzielbaren Feinzelligkeit zu achten, z.B. wird durch den Zusatz von Antioxydantien die Feinzelligkeit wieder verringert.However, compatibility with the molding composition according to the invention with regard to the achievable fine cellularity must be observed, e.g. the addition of antioxidants reduces the fine cell structure.

Die erfindungsgemäße Formmasse wird nachfolgend näher beschrieben. Bevorzugt werden teilkristalline Äthylen-Propylen-Terpolymere mit hoher Festigkeit, die auch als High Green Strength-Kautschuke bekannt sind, eingesetzt, die eine Reißfestigkeit über 8 N/mm2 bis zu 20 N/mm2 und mehr aufweisen. Die ausgewählten Äthylen-Propylen-Terpolymere sollen darüber hinaus eine sehr gute Verarbeitbarkeit aufweisen, deshalb werden Äthylen-Propylen-Terpolymere mit einer Mooney-Viskosität ML 1 +4/100 größer 50 ausgewählt. Besonders geeignet sind Äthylen-Ppropylen-Terpolymere mit 65 bis 80 Gew.-% Äthylen, 4 bis 10 Gew.-% Terkomponente und 10 bis 31 Gew.-% Propylen. Als besonders geeignet haben sich Äthylen-Propylen-Terpolymere mit einer Terkomponente aus Äthylidennorbornen oder 1,4-Hexadien erwiesen. Die gewünschte erfindungsgemäße Feinzelligkeit des vernetzten Schaumstoffes wird durch den Zusatz von Mindestmengen des ausgewählten teilkristallinen Äthylen-Propylen-Terpolymers erreicht, wobei mindestens 25 Gew.-Teile erforderlich sind bezogpn auf 100 Gew.-Teile Polyolefin. Bevorzugt werden 25 bis 60 Gew.-Teile Äthylen-Propylen-Terpolymere auf 100 Gew.-Teile Polyolefin eingesetzt. Dies ist insbesondere insoweit von Bedeutung, als beispielsweise Polyäthylen ein preiswerterer Kunststoff gegenüber einem Äthylen-Propylen-Terpolymer ist und die erfindungsgemäß herstellbaren vernetzten Polyolefinschaumstoffe mit geringerem Anteil an Äthylen-Propylen-Terpolymer wirtschaftlich sind.The molding composition according to the invention is described in more detail below. Semi-crystalline ethylene-propylene terpolymers with high strength, which are also known as high green strength rubbers, are preferably used, which have a tensile strength above 8 N / mm 2 up to 20 N / mm2 and more. The selected ethylene-propylene terpolymers should also have very good processability, which is why ethylene-propylene terpolymers with a Mooney viscosity ML 1 +4/100 greater than 50 are selected. Ethylene-propylene terpolymers with 65 to 80% by weight of ethylene, 4 to 10% by weight of ter component and 10 to 31% by weight of propylene are particularly suitable. Ethylene-propylene terpolymers with a ter component of ethylidene norbornene or 1,4-hexadiene have proven to be particularly suitable. The desired fine cell structure of the crosslinked foam according to the invention is achieved by adding minimum amounts of the selected partially crystalline ethylene-propylene terpolymer, with at least 25 parts by weight being required based on 100 parts by weight of polyolefin. 25 to 60 parts by weight of ethylene-propylene terpolymers per 100 parts by weight of polyolefin are preferably used. This is particularly important insofar as, for example, polyethylene is an inexpensive plastic compared to an ethylene-propylene terpolymer and the crosslinked polyolefin foams which can be produced according to the invention are economical with a lower proportion of ethylene-propylene terpolymer.

Ein bevorzugtes Verfahren zum Herstellen von vernetzten Schaumstoffen ist gem. der Erfindung mit sehr feiner. g)eichförmiger überwiegend geschlossener Zellstruktur auf Basis eines Gemisches von Polyolefinen und Äthylen-Propylen-Kautschuk eines Schäummittels und ggf. eines Vernetzungsmittels wird in der Weise durchgeführt, daß zunächst aus dem Polyolefin und 25 bis 150 Gew.-%, bezogen auf das Gewicht des Polyolefins eines teilkristallinen Äthylen-Propylen-Terpolymers, das eine Reißfestigkeit größer 5,0 N/mm2, eine Mooney Viskosität (ML 1 +4/100) größer 50 und einer Schmelzwärme A Hs größer 10 J/g und

  • 60 bis 80 Gew.-% Äthylen,
  • 10 bis 38 Gew.-% Propylen,
  • 2 bis 10 Gew.-% Terkomponente aus Äthylidennorbornen oder 1,4 Hexadien aufweist, sowie

einem geeigneten Schäummittel und ggf. geeignetem Vernetzungsmittels, unterhalb der Zersetzungstemperaturen von Vernetzungs- und Schäummittel hergestellt wird, wobei das Schäummittelel eine über der Zersetzungstemperatur des Vernetzungsmittels liegende Zersetzungstemperatur aufweist, und daß die Mischung dann geformt, ggf. mit energiereichen Strahlen einer Dosis von 1 bis 20 Mrad behandelt und/oder zur Vernetzung und zur Verschäumung mittels Heißluft, Strahlen und/oder Flüssigkeitsbad auf Temperaturen zwischen 200 bis 240°C erhitzt wird.A preferred method for producing cross-linked foams is gem. the invention with very fine. g) oak-shaped, predominantly closed cell structure based on a mixture of polyolefins and ethylene-propylene rubber, a foaming agent and optionally a crosslinking agent is carried out in such a way that initially from the polyolefin and 25 to 150% by weight, based on the weight of the Polyolefin of a partially crystalline ethylene-propylene terpolymer, which has a tensile strength greater than 5.0 N / mm 2 , a Mooney viscosity (ML 1 +4/100) greater than 50 and a heat of fusion AH s greater than 10 J / g and
  • 60 to 80% by weight of ethylene,
  • 10 to 38% by weight of propylene,
  • 2 to 10 wt .-% Terkompät from ethylidene norbornene or 1.4 hexadiene, and

a suitable foaming agent and, if appropriate, a suitable crosslinking agent, is produced below the decomposition temperatures of the crosslinking agent and foaming agent, the foaming agent having a decomposition temperature above the decomposition temperature of the crosslinking agent, and the mixture then being shaped, optionally with high-energy jets of a dose of 1 to 20 Mrad treated and / or heated to temperatures between 200 to 240 ° C for crosslinking and foaming by means of hot air, jets and / or liquid bath.

Ein besonderer Vorteil des erfindungsgemäßen Verfahrens ist darin zu sehen, daß ohne Anwendung von äußerem Druck oder Formen kontinuierlich Schaumstoffbahnen auf Basis von Polyolefinen und Äthylen-Propylen-Kautschuk mit sehr fein Zellen in homogener Qualität und glatter Oberfläche hergestellt werden können.A particular advantage of the process according to the invention is that foam sheets based on polyolefins and ethylene-propylene rubber with very fine cells with a homogeneous quality and smooth surface can be produced continuously without the use of external pressure or molding.

Eine weitere Verbesserung des erfindungsgemäßen Verfahrens zum Herstellen sehr feinzelliger homogener Schaumstoffe auf Basis von Polyolefinen und Äthylen-Propylen-Terpolymeren ergibt sich überraschenderweise dadurch, daß die geformte Mischung vor dem Vernetzen und Ausschäumen einer Temperaturbehandlung unterworfen wird. Diese Temperaturbehandlung kann entweder kurzfristig sein, sie wird dann bevorzugt bei einer unterhalh der Zersetzungstemperatur des Vernetzungsmittels insbesondere bei einer Temperatur zwischen etwa 90 und 110°C während 2 bis 90 Minuten durchgeführt oder aber bei Raumtemperatur, d.h. etwa 15 bis 20°C während einer Zeit von wenigstens 1 Tag. Die letztere Verfahrensweise bedeutet beispielsweise, daß die geformte Mischung gelagert werden kann, ehe sie nachfolgend der Vernetzung und Verschäumung unterworfen wird. Die Erklärung für die weitere Verbesserung des herstellbaren Schaumes in Bezug auf seine Feinzelligkeit und Homogenität könnte darin gesehen werden, daß eine sehr geringe Vernetzung durch während der Formung der homogenen Mischung freigesetzte Radikale erfolgen kann. Diese Verbesserung des herstellbaren Schaumes bezüglich Oberflächengüte und gleichmäßige Feinzelligkeit gemäß den erfindungsgemäß vorgesehenen Verfahrensschritten tritt mit steigendem Äthylen-Propylen-Terpolymer-Anteil auf.A further improvement of the process according to the invention for the production of very fine-celled homogeneous foams based on polyolefins and ethylene-propylene terpolymers surprisingly results from the fact that the shaped mixture is subjected to a temperature treatment before crosslinking and foaming. This temperature treatment can either be brief, it is then preferably carried out at below the decomposition temperature of the crosslinking agent, in particular at a temperature between about 90 and 110 ° C for 2 to 90 minutes, or at room temperature, i.e. about 15 to 20 ° C for a period of at least 1 day. The latter procedure means, for example, that the shaped mixture can be stored before it is subsequently subjected to crosslinking and foaming. The explanation for the further improvement of the foam that can be produced with regard to its fine cell structure and homogeneity could be seen in the fact that very little crosslinking can take place due to radicals released during the formation of the homogeneous mixture. This improvement of the foam that can be produced with regard to surface quality and uniform fine celling in accordance with the process steps provided according to the invention occurs with increasing ethylene-propylene-terpolymer content.

Mit dem erfindungsgemäßen Verfahren sind vernetzte Polyolefinschaumstoffe mit sehr großer Feinzelligkeit und Homogenität, geringen Wanddicken, einer geschlossenen Oberfläche sowie hoher Elastizität und Weichheit im Griff herstellbar. Des weiteren sind die Eigenschaften des mit der erfindungsgemäßen Formmasse und nach den beschriebenen Verfahren herstellbaren Schaumstoffes gegenüber Polyolefinschaumstoffen ohne Zusatz der erfindungsgemäß ausgewählten Äthylen-Propylen-Terpolymere insbesondere in Bezug auf Druckspannung, dynamische Perforation sowie Wärmeisolierung und Bruchdehnung wesentlich verbessert. Die erfindungsgemäß hergestellten Schaumstoffe können vorteilhaft eingesetzt werden für die Herstellung von Formteilen durch Vakuumverformung, da sie eine gute Wärmeverformbarkeit aufweisen sowie für anspruchsvolle Wärmeisolierungen bei erhöhten Temperaturen.The process according to the invention can be used to produce crosslinked polyolefin foams with a very high degree of fine cell and homogeneity, low wall thicknesses, a closed surface and high elasticity and softness in the handle. Furthermore, the properties of the foam which can be produced using the molding composition according to the invention and by the processes described are significantly improved compared to polyolefin foams without the addition of the ethylene-propylene terpolymers selected according to the invention, in particular with regard to compressive stress, dynamic perforation and thermal insulation and elongation at break. The foams produced according to the invention can advantageously be used for the production of molded parts by vacuum forming, since they have good heat deformability and for demanding thermal insulation at elevated temperatures.

Die erfindungsgemäß herstellbaren vernetzten Schaumstoffe weisen bei guter Temperaturbeständigkeit und sehr hoher Feinzelligkeit eine unerwartet hohe Dehnbarkeit und ausgezeichnete Verarbeitbarkeit für Vakuumverformung im Tiefziehverfahren und ähnliche Verformungsverfahren auf.The crosslinked foams which can be produced according to the invention have, with good temperature resistance and very high fine cell structure, an unexpectedly high ductility and excellent processability for vacuum deformation in the deep-drawing process and similar deformation processes.

Die erfindungsgemäße schäumbare Formmasse erfordert relativ niedrige Mengen an Vernetzungsmittel, beispielsweise Peroxyden, um eine bei der Herstellung des vernetzten Schaumstoffes ausreichende Vernetzung zu erzielen.The foamable molding composition according to the invention requires relatively low amounts of crosslinking agent, for example peroxides, in order to achieve sufficient crosslinking in the production of the crosslinked foam.

Dieser Effekt wird durch den erfindungsgemäßen Zusatz von Äthylen-Propylen-Terpolymer erreicht, da dieser leichter vernetzt als Polyolefine und daher im verglich zu reinen Polyolefinschäumen nur geringe Mengen an Vernetzungsmittel zusätzlich in der Gesamtmischung benötigt werden.This effect is achieved by the addition of ethylene-propylene terpolymer according to the invention, since this is more easily crosslinked than polyolefins and therefore, in comparison with pure polyolefin foams, only small amounts of crosslinking agent are additionally required in the overall mixture.

Ein vernetzter Schaumstoff ist in der Regel nicht zu 100 % vernetzt, sondern zwischen 40 und 80 %. Der Vernetzungsgrad wird hierbei beispielsweise bei zwölfstündiger Extraktion des vernetzten Schaumstoffes bei 135°C mit Tetrahydronaphthalin als Lösungsextraktionsmittel im Gelgehalt gemessen. Der Gelgehalt sollte dann bei den erfindungsgemäß hergestellten Schaumstoffen zwischen 40 und 80 Gew.-% liegen.A cross-linked foam is usually not 100% cross-linked, but between 40 and 80%. The degree of crosslinking is measured here, for example, when the crosslinked foam is extracted for twelve hours at 135 ° C. using tetrahydronaphthalene as the solution extractant in the gel content. The gel content in the foams produced according to the invention should then be between 40 and 80% by weight.

Die erfindungsgemäße schäumbare Formmasse ist durch die vorgesehene Auswahl von Materialien besonders gut verarbeitbar, d.h. extrudierbar, wodurch eine homogene Mischung und Formgebung der schäumfähigen Formmasse zur Bahnfolie oder zum Profil hergestellt werden kann.The foamable molding composition according to the invention is particularly easy to process due to the intended selection of materials, i.e. extrudable, so that a homogeneous mixture and shaping of the foamable molding compound can be made to the sheet or profile.

Die Erfindung wird in den nachfolgenden Beispielen näher beschriehen.The invention is described in more detail in the examples below.

Für die Prüfung von Eigenschaften wurden folgende Meßmethoden angewendet:

  • MFI (190/2) nach DIN 53 735
  • Mooney-Viskosität (ML 1 +4/100) nach DIN 53 523
  • Schmelzwärme 0 Hs im Differentialabtastcalorimeter DSC in J/g
  • Reißfestigkeit N/mm2 nach DIN 53455
  • Bruchdehnung in % nach DIN 53455
The following measurement methods were used to test properties:
  • MFI (190/2) according to DIN 53 735
  • Mooney viscosity (ML 1 +4/100) according to DIN 53 523
  • Heat of fusion 0 H s in the differential scanning calorimeter DSC in J / g
  • Tear resistance N / mm 2 according to DIN 53455
  • Elongation at break in% according to DIN 53455

Herstellung der Proben:

  • Die abgewogenen Rezepturbestandteile wurden auf einem Walzwerk bei 110°C Walzentemperatur zu einem Walzfell homogenisiert und anschließend noch 5 min. gewalzt.
Preparation of the samples:
  • The weighed recipe components were homogenized on a rolling mill at a rolling temperature of 110 ° C. to form a rolled skin and then for a further 5 minutes. rolled.

Das erhaltene Walzfell wird in der Presse bei 130°C, 50 bar und einer Stehzeit von 8 min. geglättet. Aus dieser Platte werden proben von 8 cm 0 ausgestanzt und diese dann in einem Trockenschrank bei einer Temperatur von 210°C zu Schaumkörpern ausgeschäumt. Die ungeschäumten Platten hatten eine Dicke von 4 mm.The rolled skin obtained is in the press at 130 ° C, 50 bar and a standing time of 8 min. smoothed. Samples of 8 cm 0 are punched out of this plate and these are then foamed into foam bodies in a drying cabinet at a temperature of 210 ° C. The unfoamed panels had a thickness of 4 mm.

Die Herstellung der Proben kann auch durch Mischen der Rezeptur auf kontinuierlichen Compoundieranlagen erfolgen, wobei das dann erhaltene Granulat nachfolgend auf einem Breitschlitzextruder zu einer Matrix extrudiert wird, die dann in einem beispielsweise heizbaren Kanal zu einer endlosen Schaumstoffbahn unter Vernetzung ausgeschäumt wird.The samples can also be produced by mixing the recipe on continuous compounding systems, the granules then obtained being subsequently extruded on a slot extruder to form a matrix which is then foamed in an, for example, heatable channel to form an endless foam web with crosslinking.

Beispiele 1 bis 10Examples 1 to 10

Aus Hochdruckpolyäthylen mit einem Schmelzindex MFI (190/2) von 3 g je 10 Minuten und einer Dichte von 0,92 g/cm und einem Äthylen-Propylen-Terpolymer enthaltend 70 Gew.-% Äthylen, 25 Gew.-% Propylen, 5 Gew.-% 1,4-Hexadien, einer Reißfestigkeit von 22 N/mm2, einer Mooney-Viskosität ML1 +4/100 von 87 und einer Schmelzwärme ΔHS von 25, Dicumylperoxyd 40%ig als Vernetzungsmittel und Azodicarbonamid als Schäummittel wurden gemäß den in der Tabelle 1 aufgefürten Beispielen 1 bis 10 angegebenen Gew.-Teilen Formmassen und daraus Proben in der Presse wie vorangehen beschrieben, hergestellt und zu Schaumstoffkörpern ausgeschäumt. In der beigefügten Tabelle 1 sind die erhaltenen Rohdichten der Schaumstoffkörper, ihre Oberflächengüte und die Feinzelligkeit erläutert.From high-pressure polyethylene with a melt index MFI (190/2) of 3 g each 10 minutes and a density of 0.92 g / cm and an ethylene-propylene terpolymer containing 70% by weight of ethylene, 25% by weight of propylene, 5 % By weight 1,4-hexadiene, a tensile strength of 22 N / mm 2 , a Mooney viscosity ML1 +4/100 of 87 and a heat of fusion ΔH S of 25, 40% dicumyl peroxide as crosslinking agent and azodicarbonamide as foaming agent were according to the parts by weight of molding compositions listed in Examples 1 to 10 listed in Table 1 and samples therefrom in the press as described above, produced and foamed into foam bodies. The attached bulk densities of the foam bodies, their surface quality and the fine cell structure are explained in the attached Table 1.

Die Beispiele 1, 2 und 12 sind hierbei die Vergleichsbeispiele.Examples 1, 2 and 12 are the comparative examples.

Beispiele 11 und 12Examples 11 and 12

Aus den gleichen Rezepturbestandteilen wie in Beispielen 1 bis 10 wurden proben im kontinuierlichen Verfahren hergestellt. Die Ergebnisse sind ebenfalls in Tabelle 1 dargestellt.Samples were produced in a continuous process from the same formulation components as in Examples 1 to 10. The results are also shown in Table 1.

In der beigefügten Fig. 1 sind fotografisch Querschnitte durch die hergestellten Proben dargestellt, aus denen die Zellgröße hervorgeht. Die Vergrößerung beträgt 2,5 : 1. Mit A ist die Probe gem. Beispiel 1 bezeichnet, ein normaler Polyäthylenschaumstoff mit Rohdichte von 30 kg/m3 ohne EPDM und gem. B der erfindungsgemäß hergestellte Schaumstoff aus einer Formmasse mit Zusatz von 30 Gew.-Teilen EPDM, Raumgewicht 38 kg/m3 nach Beispiel 3. Dieser Schaumstoff ist sehr feinzellig und weist eine glatte Oberfläche auf.In the attached FIG. 1, cross sections through the samples produced are shown, from which the cell size is shown. The magnification is 2.5: 1. With A the sample is gem. Example 1, a normal polyethylene foam with bulk density of 30 kg / m 3 without EPDM and gem. B the foam produced according to the invention from a molding composition with the addition of 30 parts by weight of EPDM, density 38 kg / m 3 according to Example 3. This foam is very fine-celled and has a smooth surface.

In der beigefügten Tabelle 2 sind die Beispiele 13 bis 22 aufgeführt, die ausgehend von einer gleichen Mischung von Hochdruckpolyäthylen und EPDM mit Vernetzungsmittel lediglich die Schäummittelmengen variieren, wodurch Schaumstoffkörper verschiedener Hohdichten hergestellt werden. In allen Fällen zeigt sich, daß die gewünschte Feinzelligkeit herstellbar ist bei glatter Oberfläche. Die eingesetzten Rohstoffe entsprechen in ihrer Qualifikation den in Beispielen 1 bis 10 beschriebenen Rohstoffen.In the attached Table 2, Examples 13 to 22 are listed, which, starting from the same mixture of high-pressure polyethylene and EPDM with crosslinking agent, only vary the amounts of foaming agent, as a result of which foam bodies of different high densities are produced. In all cases it can be seen that the desired fine cell structure can be produced with a smooth surface. The raw materials used correspond in their qualifications to the raw materials described in Examples 1 to 10.

In der Tabelle 3 sind die Eigenschaften eines vernetzten Polyäthylenschaumstoffes ohne EPDM-Zusatz mit einer Rohdichte von 130 kg/m3 des Vergleichsbeispiels 12 mit einem erfindungsgemäßen Schaumstoffkörper enthaltend 30 Gew.-Tle. EPDM auf 100 Gew.-Teile Polyäthylen bei gleicher Rohdichte gemäß Beispiel 11, zusammengestellt. Hieraus geht hervor, daß bei vergleichbaren Schaumstoffen, nämlich gleicher Rohdichte, die erfindungsgemäßen Schaumstoffe wesentlich bessere Eigenzchaften bezüglich der Festigkeit und Dehnbarkeit und Elastizität aufweisen. Die erfindungsgemäßen Schaumstoffe eignen sich daher vorzüglich für die Herstellung von Formteilen beispielsweise durch Vakuumverformen, Tiefziehverformen usw. Darüber hinaus haben sie verbesserte Isoliereigenschaften.Table 3 shows the properties of a crosslinked polyethylene foam without EPDM addition with a bulk density of 130 kg / m 3 of Comparative Example 12 with a foam body according to the invention containing 30 parts by weight. EPDM compiled on 100 parts by weight of polyethylene with the same bulk density according to Example 11. It follows from this that with comparable foams, namely the same bulk density, the foams according to the invention have significantly better properties with regard to strength and extensibility and elasticity. The foams according to the invention are therefore particularly suitable for the production of molded parts, for example by vacuum forming, deep-drawing molding, etc. In addition, they have improved insulating properties.

Beispiele 23 bis 26Examples 23-26

Aus 100 Gew.-Teilen Hochdruckpolyäthylen mit einem Schmelzindex MFI (190/2) von 3 g je 10 Min. und einer Dichte von 0,92 g/cm3, 2,3 Gew.-Teilen 40 %igem Dicuomylperoxyd, 19 Gew.-Teilen Azodicarbonamid sowie Mengen von 20 bzw. 40 bzw. 60 bzw. 80 Gew.-Teilen eines Äthylen-Propylen-Terpolymers enthaltend 67 Gew.- % Äthylen, 27 Gew.-% Propylen und 6 Gew.-% Äthylennorbornen mit einer Mooney-Viskosität ML 1 +4/100 von 85 und einer Schmelzwärme AH, von 14 J/g und einer Reißfestigkeit von 11,2 N/mm2 wurden Schumstoffkörper hergestellt. Erst die Proben mit 40 und mehr Gew.-Teilen EPDM zeigten sehr gute Feinzelligkeit und eine glatte Oberfläche. Die Rohdichten der Schaumstoffkörper betrugen 31, 35, 41, 45 kg/m3. Das Beispiel 23 mit 20 Gew.-Teilen Äthylen-Terpolymer ist ein Vergleichsbeispiel.From 100 parts by weight of high-pressure polyethylene with a melt index MFI (190/2) of 3 g each 10 min. And a density of 0.92 g / cm3, 2.3 parts by weight of 40% dicuomyl peroxide, 19 parts by weight. Parts of azodicarbonamide and quantities of 20 or 40 or 60 or 80 parts by weight of an ethylene-propylene terpolymer containing 67% by weight of ethylene, 27% by weight of propylene and 6% by weight of ethylene norbornene with a Mooney Viscosity ML 1 +4/100 of 85 and a heat of fusion AH, of 14 J / g and a tensile strength of 11.2 N / mm 2 were made of foam bodies. Only the samples with 40 or more parts by weight of EPDM showed very good fine cell structure and a smooth surface. The bulk densities of the foam bodies were 31, 35, 41, 45 kg / m 3. Example 23 with 20 parts by weight of ethylene terpolymer is a comparative example.

Vergleichs-Beispiele 27 bis 30:Comparative Examples 27 to 30:

Aus 100 Gew.-Teilen Hochdruckpolyäthylen MFI 190/2 von 3 g je 10 Min., 19 Gew.-Teilen Azodicarbonamid, 2,3 Gew.-Teilen 40 %igem Dicumylperoxyd wurden Mischungen hergestellt mit Zusatz von 20 bzw. 40, 60, 80 Gew.-Teilen eines Äthylen-Propylen-Kautschukes mit 70 bis 76 % Äthylen und 24 bis 30 % Propylen, einer Mooney-Viskosität ML 1 +4/100 von 85 und einer Schmelzwärme A HS von 21 J/g und einer Reißfestigkeit von 5,8 N/mm2. Hieraus wurden Schaumstoffkörper hergestellt, die jedoch eine rauhe Oberfläche aufwiesen und nicht feinzellig waren, sondern in der Qualität den nach Fig. 1 Abbildung A dargestellten entsprachen. Die eingesetzten Äthylen-Propylen-Kautschuke entsprachen nicht der erfindungsgemäß vorgesehenen Qualifikation.Mixtures were prepared from 100 parts by weight of high-pressure polyethylene MFI 190/2 of 3 g each for 10 minutes, 19 parts by weight of azodicarbonamide, 2.3 parts by weight of 40% dicumyl peroxide, with the addition of 20 or 40, 60, 80 Parts by weight of an ethylene-propylene rubber with 70 to 76% ethylene and 24 to 30% propylene, a Mooney viscosity ML 1 +4/100 of 85 and a heat of fusion AH S of 21 J / g and a tensile strength of 5 .8 N / mm 2 . Foam bodies were produced from this, but they had a rough surface and were not fine-celled, but corresponded in quality to that shown in FIG. 1, Figure A. The ethylene-propylene rubbers used did not meet the qualification provided for by the invention.

Beispiele 31 und 32Examples 31 and 32

Aus 100 Gew.-Teilen Hochdruckpolyäthylen MFI 190/2 von 3 g je 10 min, 19 Gew.-Teilen Azodicarbonamid und 2,3 Gew.-Teilen 40 %igem Dicumylperoxyd wurden zusammen mit 40 bzw. 80 Gew.-Teilen eines Äthylen-Propylen-Kautschukes enthaltend 54 Gew.-% Äthylen, 42 Gew.-% Propylen, 4 Gew.-% Äthylidennorbornen, mit einer Mooney-Viskosität ML 1 +4/100 von etwa 94, einer Schmelzwärme A Hs von 0 (amorpher Zustand), einer Reißfestigkeit von 0,162, Proben hergestellt, die jedoch ebenfalls nicht feinzellig wurden, sondern grobzellig mit rauher Oberfläche. Die erzielten Rohdichten lagen hei 38, 45 und 50 kg/m2.100 parts by weight of high-pressure polyethylene MFI 190/2 of 3 g per 10 min, 19 parts by weight of azodicarbonamide and 2.3 parts by weight of 40% dicumyl peroxide were mixed with 40 or 80 parts by weight of an ethylene Propylene rubber containing 54% by weight of ethylene, 42% by weight of propylene, 4% by weight of ethylidene norbornene, with a Mooney viscosity ML 1 +4/100 of about 94, a heat of fusion AH s of 0 (amorphous state) , a tensile strength of 0.162, produced samples which, however, also did not become fine-celled, but rather coarse-celled with a rough surface. The bulk densities achieved were 38, 45 and 50 kg / m 2 .

Wie bereits vorangehend ausgeführt, ist die erzielbare Zellgröße, und damit Zellstruktur des Schaumstoffes sowohl abhängig von der Rezeptur, d.h. den Rezepturbestandteilen, als auch von der zu schäumenden Schaumkörpergröße. Die erzielbare Zellgröße ist immer abhängig von der Raumdichte des herzustellenden Schaumstoffes und von der Dicke der geformten noch nicht aufgeschäumten Mischung. Hierbei ist es so, daß mit steigender Raumdichte bei sonst konstanten Parametern die Zellen immer kleiner werden. Hingegen werden bei größer werdender Dicke der noch nicht geschäumten geformten Mischung die Zellen immer größer bei sonst gleichen Parametern.As already explained above, the achievable cell size, and thus the cell structure of the foam, is dependent both on the formulation, i.e. the recipe components, as well as the foam body size to be foamed. The cell size that can be achieved always depends on the density of the foam to be produced and on the thickness of the mixture which has not yet been foamed. It is the case that with increasing spatial density and otherwise constant parameters, the cells become smaller and smaller. On the other hand, as the thickness of the molded mixture which has not yet been foamed increases, the cells become ever larger with the same parameters.

In der beigefügten Fig. 2 ist die Abhängigkeit der erzielbaren mittleren Zelldurchmesser von der Raumdichte eines Polyolefinschaumes ohne (Kurve I) und mit erfindungsgemäße Zusatz von 40 Gew. Äthylen-Propylen-Terpolymer (Kurve II) wie in den Beispielen 1 bis 10 beschrieben, dargestellt bei einer Dicke der geformten noch nicht ausgeschäumten Platte von 4 mm.

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
 The attached FIG. 2 shows the dependence of the achievable average cell diameter on the bulk density of a polyolefin foam without (curve I) and with the addition according to the invention of 40% by weight of ethylene-propylene terpolymer (curve II) as described in Examples 1 to 10 at a thickness of the molded, not yet foamed sheet of 4 mm.
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004

Claims (13)

1. Foamable moulding composition for the production of a cross-linked foam material from a mixture of a polyolefin, an ethylene-propylene rubber, a foaming agent and, optionally, a cross-linking agent, by foaming in the absence of applied pressure, characterised in that it contains, per 100 parts by weight of polyolefin,
25 to 150 parts by weight of a partially crystalline ethylene-propylene terpolymer having a tear resistance greater than 5.0 N/mm2, a Mooney viscosity (ML 1 +4/100) greater than 50, with a melting heat (according to DSC) of at least A Hs 10 J/g with contents of
60 to 80 % by weight ethylene
2 to 10% by weight tercomponent of ethylidenenorbornene or 1,4-hexadiene
10 to 38% by weight propylene.
2. Moulding composition according to claim 1, characterised in that the ethylene-propylene terpolymer contains
65 to 80% by weight ethylene
4 to 10% by weight of tercomponent
10 to 31% by weight of propylene
and has a tear resistance above 8 N/mm2.
3. Moulding composition according to one of claims 1 or 2, characterised in that the mixture contains 25 to 60 parts by weight of ethylene-propylene terpolymer per 100 parts by weight of polyolefin.
4. Moulding composition according to claim 1, characterised in that a polyethylene with a melt index (MFI 190/2) of 1 to 8 and a density of 0.91 to 0.96 g/cm3 is provided as polyolefin.
5. Moulding composition according to one of claims 1 to 4, characterised in that the mixture contains, per 100 parts by weight of polyolefin and 25 to 150 parts by weight of ethylene-propylene terpolymer, 0.6 to 1.6 parts by weight of a peroxidic cross-linking agent.
6. Moulding composition according to claim 5, characterised in that dicumyl peroxide is provided as peroxide.
7. Moulding composition according to one of claims 1 to 6, characterised in that there is provided a foaming agent with higher decomposition temperature than the cross-linking agent, in particular azodicarbonamide, dinitroso-pentamethylenetetramine, p,p'-oxy-bis-benzenesulphonylhydrazide, tolulenesulphonylhydrazide.
8. Process for the production of cross-linked foam materials with very fine uniform predominantly closed cell structure from a mixture of a polyolefin, an ethylene-propylene rubber, a foaming agent and, optionally, a cross-linking agent, characterised in that firstly a homogeneous mixture of 100 parts by weight of polyolefin and 25 to 150 parts by weight of partially crystalline ethylene-propylene terpolymer which has a tear resistance greater than 5.0 N/mm2, a Mooney viscosity (ML 1 +4/100) greater than 50 and a melting heat A Hs (according to DSC) greater than 10 J/g as well as contents of
60 to 80% by weight ethylene,
10 to 38% by weight propylene,
2 to 10% by weight of tercomponent of ethylidenenorbornene or 1,4-hexadiene,

as well as a suitable foaming agent and optionally suitable cross-linking agent, is produced below the decomposition temperature of the cross-linking and foaming agents, with the foaming agent having a decomposition temperature lying above the decomposition temperature of the cross-linking agent, and that the mixture is then shaped, optionally treated with energy-rich irradiation in a dose of 1 to 20 Mrad and/or is heated for cross-linking and for foaming to temperatures between 200 to 240°C by means of heated air, irradiation and/or a liquid bath.
9. Process according to claim 8, characterised in that there is used an ethylene-propylene terpolymer with a tear resistance of at least 8 N/mm2 containing
65 to 80% by weight of ethylene,
10 to 31% by weight of propylene,
4 to 10% by weight of tercomponent.
10. Process according to claim 9, characterised in that a polyethylene with a melt index (MFI 190/2) of 1 to 8 and a density of 0.91 to 0.96 g/cm3 is used as polyolefin.
11. Process according to one of claims 8 to 10, characterised in that a peroxide, in particular dicumyl peroxide, is added in an amount of 0.6 to 1.6 parts by weight referred to 100 parts by weight of polyolefin and 25 to 150 parts by weight of ethylene-propylene terpolymer, for chemical cross-linking.
12. Process according to claim 11, characterised in that the shaped mixture is tempered before the cross-linking and foaming at a temperature below the decomposition temperature of the cross-linking agent, in particular at a temperature between about 90 and 110° C, over 2 to 90 minutes.
13. Process according to claim 11, characterised in that the shaped mixture is tempered before the cross-linking and foaming at about 15 to 20°C for a period of at least one day.
EP82106447A 1981-08-17 1982-07-17 Moulding composition for a cross-linked foam of polyolefins and ethylene-propylene rubber, and process for producing the foam Expired EP0072444B1 (en)

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